CN106589458B - A kind of fire retardant and its application and resistance combustion polyurethane foam and preparation method thereof - Google Patents
A kind of fire retardant and its application and resistance combustion polyurethane foam and preparation method thereof Download PDFInfo
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- CN106589458B CN106589458B CN201611128268.9A CN201611128268A CN106589458B CN 106589458 B CN106589458 B CN 106589458B CN 201611128268 A CN201611128268 A CN 201611128268A CN 106589458 B CN106589458 B CN 106589458B
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- fire retardant
- flyash
- polyurethane foam
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 93
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 62
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 61
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000010881 fly ash Substances 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 59
- 239000010439 graphite Substances 0.000 claims abstract description 55
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010883 coal ash Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical group COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to polyurethane foam flame retardant area, a kind of fire retardant and its application and resistance combustion polyurethane foam and preparation method thereof are disclosed.The fire retardant contains expansible graphite and flyash, and the weight ratio of expansible graphite and the flyash is (1~5)：1.The resistance combustion polyurethane foam for making coal ash lifting Gong obtain has excellent flame retardant property.
Description
Technical field
The present invention relates to polyurethane foam flame retardant areas, and in particular, to a kind of fire retardant and its in polyurethane foam
Application and a kind of resistance combustion polyurethane foam and preparation method thereof.
Background technique
Rigid polyurethane foam is a kind of high molecular material with excellent thermal insulation effect, high specific strength, is answered extensively
For the industries such as build, freeze.
It is halogen containing flame-retardant commonly used in improving the fire retardant of flame retardant of plastic performance, but at present it was recognized that such resistance
Combustion agent causes to seriously endanger to environmental and biological materials.Therefore halogen-free flame retardants how is provided for rigid polyurethane foam
It is fire-retardant to become research hotspot.
《Research of the expansible graphite in hard polyurethane foams flame retardant property》(Hu Xingsheng, Hao Jianwei, plastics, 2004
The phase of volume 33 the 1st year, 45-47 pages) flame retardant property of the expansible graphite in rigid polyurethane foam has been investigated, referred to using oxygen
Number has studied expansible graphite and ammonium polyphosphate (APP), triethyl phosphate (TEP), melamine (MA), melamine cyanurate
Fire retardation of the salt (MCA) to polyurethane foam.
《The Effects of Intumescent Flame Retardant Including Ammonium
Polyphosphae/Pentaerythritol and Fly Ash Fillers on the Physicomechanical
Properties of Rigid Polyurethane Foams》(Ali Riza Tarakcilar,Journal of
Applied Polymer Science, Vol.120,2095-2102 (2011)) report ammonium polyphosphate and pentaerythrite expansion
The flyash of system and 5wt% are used cooperatively, to the flame retardant property of rigid polyurethane foam.
But there is still a need for how to make good use of flyash, provide the polyurethane foam with more preferable flame retardant property.
Summary of the invention
The purpose of the invention is to so that polyurethane foam is had better flame resistance using flyash and make good use of powder
Coal ash provides a kind of fire retardant and its application and resistance combustion polyurethane foam and preparation method thereof.
To achieve the goals above, the present invention provides a kind of fire retardant, wherein the fire retardant contains expansible graphite and powder
The weight ratio of coal ash, expansible graphite and the flyash is (1~5)：1.
The present invention also provides a kind of application of fire retardant of the invention in polyurethane foam.
The present invention also provides a kind of resistance combustion polyurethane foams, wherein using the total weight of the resistance combustion polyurethane foam as base
Standard, the resistance combustion polyurethane foam contain the fire retardant of 29~43 weight %, the polyurethane of 57~71 weight %；The fire retardant contains
There are an expansible graphite and flyash, the weight ratio of expansible graphite and the flyash is (1~5)：1.
The present invention also provides a kind of method for preparing resistance combustion polyurethane foam, this method includes：It will be containing catalyst, more
First alcohol, foam stabiliser, foaming agent and fire retardant component A, reacted with the component B containing isocyanates；It is described fire-retardant
Agent contains expansible graphite and flyash, and the weight ratio of expansible graphite and the flyash is (1~5)：1.
Through the above technical solutions, the present invention provides a kind of fire retardant containing expansible graphite and flyash, it can be swollen
There can be synergy at fire-retardant aspect according to the mixing of specific ratio between swollen graphite and flyash, can preferably utilize
Flame retardant property of the coal ash lifting for polyurethane foamed material.
The present invention can also make flyash increase new purposes.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first object of the present invention provides a kind of fire retardant, wherein and the fire retardant contains expansible graphite and flyash,
The weight ratio of expansible graphite and the flyash is (1~5)：1.
Preferably, the weight ratio of expansible graphite and the flyash is (1~4.9)：1.
According to the present invention, it when being prepared between expansible graphite and the flyash according to aforementioned proportion, can mutually cooperate with,
More efficiently flame retardant effect is provided.When the configuration proportion of expansible graphite and the flyash not within the above range when, use
Effective flame retardant effect cannot be obtained in resistance combustion polyurethane foam.Under preferable case, on the basis of the total weight of the fire retardant,
The content of expansible graphite is 50~83 weight % in the fire retardant, and the content of the flyash is 17~50 weight %.
In the present invention, a kind of preferred embodiment, in the fire retardant, on the basis of the total weight of the fire retardant,
The content of expansible graphite is 50~83 weight %, and the content of the flyash is 17~50 weight %；Expansible graphite and institute
The weight ratio for stating flyash is (1~5)：1, preferably (1~4.9)：1.
It is 90~99.9 weight % that carbon content is fixed in the case of, according to the invention it is preferred to, in expansible graphite, and water content is
1 weight % or less.Expansible graphite is known substance, can commercially available Qingdao day and graphite Co., Ltd product, fixed carbon contains
Amount is 99 weight %, and water content is 0.5 weight %.
In the case of, according to the invention it is preferred to, the flyash is obtained solid particle after coal combustion, the flyash
Average grain diameter is 30 μm or less；On the basis of the total weight of the flyash, the flyash contains 60 weight % or more
SiO2And Al2O3.It selects flyash to meet above-mentioned condition, can have with expansible graphite and preferably coordinate to match, providing more has
The flame retardant effect of effect.Such as can the specifically used flyash from Guohua Electric Power company Beijing Thermal Power Plant, average grain diameter be 3 μ
M, group become：The SiO of 41.25 weight %2, the Al of 35.58 weight %2O3, the CaO of 10.14 weight %, 5.94 weight %'s
Fe2O3。
The second object of the present invention provides a kind of application of fire retardant of the invention in polyurethane foam.Use this hair
Bright fire retardant can provide polyurethane foam with good flame retardant property, and realize the utilization of flyash.
The third object of the present invention, as a preferred embodiment, providing a kind of resistance combustion polyurethane foam, wherein
On the basis of the total weight of the resistance combustion polyurethane foam, fire retardant containing 29~43 weight % in the resistance combustion polyurethane foam,
The polyurethane of 57~71 weight %；The fire retardant contains expansible graphite and flyash, expansible graphite and the flyash
Weight ratio be (1~5)：1.
In resistance combustion polyurethane foam provided by the invention, the fire retardant contains expansible graphite and flyash according to above-mentioned
When proportional region is prepared, effective flame retardant effect could be obtained for resistance combustion polyurethane foam.
Preferably, on the basis of the total weight of the fire retardant, in the fire retardant content of expansible graphite be 50~
83 weight %, the content of the flyash are 17~50 weight %.Expansible graphite is known substance, can commercially available Qingdao day and
The product of graphite Co., Ltd obtains.The flyash is obtained solid particle after coal combustion, the average grain of the flyash
Diameter is 30 μm or less；On the basis of the total weight of the flyash, the flyash contains the SiO of 60 weight % or more2With
Al2O3。
In the present invention, a kind of preferred embodiment, in the resistance combustion polyurethane foam, with the total weight of the fire retardant
On the basis of, the content of expansible graphite is 50~83 weight %, and the content of the flyash is 17~50 weight %；Inflatable stone
The black weight ratio with the flyash is (1~5)：1, preferably (1~4.9)：1.
In the case of, according to the invention it is preferred to, the flame retardant property of the resistance combustion polyurethane foam is UL94V0 grade.The resistance
Combustion performance can be measured by UL-94 method.
The fourth object of the present invention, provides a kind of method for preparing resistance combustion polyurethane foam, and this method includes：It will contain and urge
Agent, polyalcohol, foam stabiliser, foaming agent and fire retardant component A, reacted with the component B containing isocyanates；Institute
It states fire retardant and contains expansible graphite and flyash, the weight ratio of expansible graphite and the flyash is (1~5)：1.
Preferably, on the basis of the total weight of the fire retardant, in the fire retardant content of expansible graphite be 50~
83 weight %, the content of the flyash are 17~50 weight %.Expansible graphite is known substance, can commercially available Qingdao day and
The product of graphite Co., Ltd obtains.The flyash is obtained solid particle after coal combustion, the average grain of the flyash
Diameter is 30 μm or less；On the basis of the total weight of the flyash, the flyash contains the SiO of 60 weight % or more2With
Al2O3。
In the present invention, a kind of preferred embodiment, in the resistance combustion polyurethane foam, with the total weight of the fire retardant
On the basis of, the content of expansible graphite is 50~83 weight %, and the content of the flyash is 17~50 weight %；Inflatable stone
The black weight ratio with the flyash is (1~5)：1, preferably (1~4.9)：1.
In the present invention, the polyalcohol can be polyalcohol commonly used in the art, such as can be polyester polyol
And/or polyether polyol.It is highly preferred that the polyalcohol is polyether polyol, it is such as selected from polypropylene oxide alcohol and/or epoxy third
The alcohol of alkane sealing end, for example, the two of polyoxypropyleneglycol, polypropylene oxide triol, polypropylene oxide tetrol, propylene oxide sealing end
At least one of alcohol, tetrol of three pure and mild propylene oxide sealing ends of propylene oxide sealing end.Preferably, the polyether polyol
Hydroxyl value is 280~440mgKOH/g.The polyalcohol is known substance, such as can the limited public affairs of commercially available Jiangsu Lv Yuan new material
The product of department obtains.
In the present invention, the isocyanates can be isocyanates commonly used in the art, such as can be diphenyl
At least one of methylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) and poly isocyanate.The isocyanide
Acid esters is known substance, for example, can the product of commercially available Guangzhou Li Tai thermal insulation material Science and Technology Ltd. obtain.
In the present invention, the foaming agent can be water and/or penta for obtaining the foaming structure of polyurethane in the reaction
Alkane.
In the present invention, the foam stabiliser can be used for the foaming foam that temperature is formed in the reaction and uniformly divide
Cloth.Preferably organic silicon surfactant can be dimethyl silicone polymer and/or silicone oil.
According to the present invention, the reaction is mainly the isocyanates in the polyalcohol and the component B in the component A,
Reaction is carried out under the action of the catalyst forms polyurethane；Foaming agent generates foaming effect simultaneously, forms foaming structure；And
And the foam stabiliser described in the reaction process stablizes foam and foam is made to be evenly distributed.
According to the present invention, as long as flame retardant polyurethane bubble is prepared in the dosage satisfaction of each component in the component A and component B
Foam.Under preferable case, relative to the polyalcohol of 100 parts by weight, the additional amount of fire retardant is 100~150 parts by weight, isocyanide
The additional amount of acid esters is 100~150 parts by weight；The additional amount of the foam stabiliser is 1~9 parts by weight, the foaming agent
Additional amount is 1~9 parts by weight.
According to the present invention, the catalyst includes stanniferous element compound and amine-containing based compound.It is described to contain tin element
Closing object can be tin catalyst commonly used in the art, it is preferable that the stanniferous element compound is urged selected from organic tin
Agent, more preferably stannous octoate and/or dibutyl tin dilaurate.The amine-containing based compound, which can be this field, routinely to be made
Amines catalyst, it is preferable that the amine-containing based compound be triethanolamine, diethanol amine and triethylene diamine at least
It is a kind of.At least one can be added using amines catalyst.
In the case of, according to the invention it is preferred to, relative to the polyalcohol of 100 parts by weight, the stanniferous element compound adds
Entering amount is 0.05~1 parts by weight, and the additional amount of the amine-containing based compound is 1~5 parts by weight.
According to the present invention, the condition of the reaction can not be particularly limited, under preferable case, the temperature of the reaction
It is 60~70 DEG C, time of the reaction is 10~for 24 hours.
The present invention will be described in detail by way of examples below.
Burning examination is carried out to the resistance combustion polyurethane foam prepared in following embodiment and comparative example according to the method for UL-94
It tests.
Flyash comes from Guohua Electric Power company Beijing Thermal Power Plant, and average grain diameter is 3 μm, and group becomes：41.25 weight %'s
SiO2, the Al of 35.58 weight %2O3, the CaO of 10.14 weight %, the Fe of 5.94 weight %2O3。
Expansible graphite is 99 weight %, water content 0.5 from Qingdao day and graphite Co., Ltd, fixed carbon content
Weight %.
In following embodiment, can as prepare raw material during resistance combustion polyurethane foam feed intake determine made from it is fire-retardant
The content of each component in polyurethane foam.
Embodiment 1
This example demonstrates that fire retardant of the invention and the method for preparing resistance combustion polyurethane foam.
(1) fire retardant is prepared
The flyash of 50 parts by weight and the expansible graphite of 50 parts by weight are uniformly mixed, fire retardant S1 is obtained.
(2) resistance combustion polyurethane foam is prepared
By the fire retardant of the polyether polyol 4110 (hydroxyl value is 430 ± 10mgKOH/g) of 100 parts by weight, 150 parts by weight
S1, the dibutyl tin dilaurate of 0.5 parts by weight, the silicone oil of 2 parts by weight, the water of 2 parts by weight, 1 parts by weight triethylene diamine
It is uniformly mixed with the triethanolamine of 3 parts by weight, obtains mixed component A1.
The mixed component A1 is mixed with the diphenylmethylene diisocyanate (MDI) of 100 parts by weight, and 70
DEG C, react 24 hours under normal pressure, obtain resistance combustion polyurethane foam PU1, wherein the content of fire retardant S1 is 43 weight %.
Embodiment 2
This example demonstrates that the method for fire retardant of the invention and preparation polyurethane foam.
(1) fire retardant is prepared
The flyash of 17 parts by weight and the expansible graphite of 83 parts by weight are uniformly mixed, fire retardant S2 is obtained.
(2) resistance combustion polyurethane foam is prepared
By the fire retardant of the polyether polyol 4110 (hydroxyl value is 430 ± 10mgKOH/g) of 100 parts by weight, 120 parts by weight
S2, the dibutyl tin dilaurate of 0.05 parts by weight, the silicone oil of 9 parts by weight, the water of 1 parts by weight, 2 parts by weight triethylene diamine
It is uniformly mixed with the triethanolamine of 3 parts by weight, obtains mixed component A2.
The mixed component A2 is mixed with the diphenylmethylene diisocyanate (MDI) of 150 parts by weight, and 60
DEG C, react 24 hours under normal pressure, obtain resistance combustion polyurethane foam PU2, wherein the content of fire retardant S2 is 29 weight %.
Embodiment 3
This example demonstrates that the method for fire retardant of the invention and preparation polyurethane foam.
(1) fire retardant is prepared
The flyash of 40 parts by weight and the expansible graphite of 60 parts by weight are uniformly mixed, fire retardant S3 is obtained.
(2) resistance combustion polyurethane foam is prepared
By the fire retardant of the polyether polyol 4110 (hydroxyl value is 430 ± 10mgKOH/g) of 100 parts by weight, 150 parts by weight
S3, the dibutyl tin dilaurate of 1 parts by weight, the silicone oil of 1 parts by weight, the pentane of 9 parts by weight, 1 parts by weight triethylene diamine
It is uniformly mixed with the triethanolamine of 1 parts by weight, obtains mixed component A3.
The mixed component A3 is mixed with the diphenylmethylene diisocyanate (MDI) of 120 parts by weight, and 70
DEG C, react 24 hours under normal pressure, obtain resistance combustion polyurethane foam PU3, wherein the content of fire retardant S3 is 31 weight %.
Comparative example 1
According to the method for embodiment 1, unlike, expansible graphite is replaced with DMMP (dimethyl methyl phosphonate), thus
Polyurethane foam DPU1 is made.
Comparative example 2
According to the method for embodiment 1, unlike, fly ash content is 0 in fire retardant, and expansible graphite content is
100%, so that polyurethane foam DPU2 be made.
Comparative example 3
According to the method for embodiment 1, unlike, fly ash content is 100% in fire retardant, and expansible graphite content is
0, so that polyurethane foam DPU3 be made.
Comparative example 4
According to the method for embodiment 1, unlike, fly ash content is 10% in fire retardant, and expansible graphite content is
90%, so that polyurethane foam DPU4 be made.
Comparative example 5
According to the method for embodiment 1, unlike, fly ash content is 90% in fire retardant, and expansible graphite content is
10%, so that polyurethane foam DPU5 be made.
Test case
By resistance combustion polyurethane foam PU1, PU2, PU3 and DPU1, DPU2, DUP3, DPU4, DPU5 according to UL-94 standard into
The test of row flame retardant property, specifically, it is 13.0 ± 0.5mm, length that polyurethane foamed material, which is formed with a thickness of 1.6mm, width,
For the test sample of 125 ± 5mm, the length of flame of burner is 20mm, implements the sample test of 2 × 10s, and according to table 1
The UL-94 test class of the shown each sample of standard determination.
The polyurethane foamed material test result of embodiment and comparative example preparation is as shown in table 2.
Table 1UL-94 testing standard
| Grade | Flame height | The maximum combustion time | Maximum total burning time | Cotton burning |
| V-0 | 3/4” | 10s | 50s(F) | Nothing |
| V-1 | 3/4” | 30s | 250s(F) | Nothing |
| V-2 | 3/4” | 30s | 250s(F) | Allow |
| NR does not have grade | 3/4” | >30s | >250 | Allow |
Table 2UL94 test result
In above-mentioned table 2, it can be seen that flyash by embodiment 1-3 to be compared with comparative example 1-5 and may expand
The fire retardant that graphite cooperation is used as polyurethane foam has synergy, and composition can use flyash and show excellent resistance
Fuel efficiency fruit reaches the V0 grade in UL-94 grade.
Expansible graphite or flyash are used alone in comparative example 2,3, uses expansible graphite and fine coal in comparative example 4,5
Ash combination cannot form the synergistic effect of expansible graphite and flyash, cannot obtain pair not within restriction of the invention
The effective flame retardant effect of polyurethane foam.
Claims (10)
1. a kind of fire retardant, which is characterized in that the fire retardant contains expansible graphite and flyash, expansible graphite and the powder
The weight ratio of coal ash is (1.5~5)：1.
2. fire retardant according to claim 1, wherein on the basis of the total weight of the fire retardant, in the fire retardant
The content of expansible graphite is 60~83 weight %, and the content of the flyash is 17~40 weight %.
3. fire retardant according to claim 1 or 2, wherein fixing carbon content in expansible graphite is 90~99.9 weights
% is measured, water content is 1 weight % or less；The flyash is obtained solid particle after coal combustion, and the flyash is averaged
Partial size is 30 μm or less；On the basis of the total weight of the flyash, the flyash contains the SiO of 60 weight % or more2With
Al2O3。
4. application of the fire retardant in polyurethane foam described in a kind of any one of claim 1-3.
5. a kind of resistance combustion polyurethane foam, which is characterized in that on the basis of the total weight of the resistance combustion polyurethane foam, this is fire-retardant poly-
Urethane foam contains the fire retardant of 29~43 weight %, the polyurethane of 57~71 weight %；The fire retardant contains inflatable stone
The weight ratio of ink and flyash, expansible graphite and the flyash is (1.5~5)：1.
6. resistance combustion polyurethane foam according to claim 5, wherein the flame retardant property of the resistance combustion polyurethane foam is
UL94V0 grade.
7. a kind of method for preparing resistance combustion polyurethane foam, this method include：Will containing catalyst, polyalcohol, foam stabiliser,
The component A of foaming agent and fire retardant is reacted with the component B containing isocyanates；The fire retardant contains expansible graphite
And flyash, the weight ratio of expansible graphite and the flyash are (1.5~5)：1.
8. according to the method described in claim 7, wherein, relative to the polyalcohol of 100 parts by weight, the additional amount of the fire retardant
For 100~150 parts by weight, the additional amount of isocyanates is 100~150 parts by weight, the additional amount of the foam stabiliser is 1~
9 parts by weight, the additional amount of the foaming agent are 1~9 parts by weight.
9. according to the method described in claim 7, wherein, the catalyst includes stanniferous element compound and amino-contained chemical combination
Object；Relative to the polyalcohol of 100 parts by weight, the additional amount of the stanniferous element compound is 0.05~1 parts by weight, described amine-containing
The additional amount of based compound is 1~5 parts by weight.
10. the method according to any one of claim 7-9, wherein the temperature of the reaction is 60~70 DEG C, described
The time of reaction be 10~for 24 hours.
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| CN1724577A (en) * | 2004-07-23 | 2006-01-25 | 四川大学 | Preparation of expandable graphite filled high dendensity hard polyurethane foamed plastic |
| CN101802131A (en) * | 2007-05-18 | 2010-08-11 | 攀高维度材料公司 | Flame resistant and heat protective flexible material with intumescing guard plates and method of making the same |
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| CN1724577A (en) * | 2004-07-23 | 2006-01-25 | 四川大学 | Preparation of expandable graphite filled high dendensity hard polyurethane foamed plastic |
| CN101802131A (en) * | 2007-05-18 | 2010-08-11 | 攀高维度材料公司 | Flame resistant and heat protective flexible material with intumescing guard plates and method of making the same |
| CN104774313A (en) * | 2014-01-09 | 2015-07-15 | 神华集团有限责任公司 | Fire retardant, polyurethane foam material, and preparation method of fire retardant and polyurethane foam material |
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